DE1694412A1 - Bulk dyeing process for synthetic linear polyesters - Google Patents

Description

L ..- JHG. ri. ri'lCZZ .PL.-JNG. H. tiOHR! IPL.-1NG. S. STAEGER

description

to the patent application of. | gft # JlIJi

Imperial Chemical Industries Limited, London, S, W. "I.,

concerned

Process for coloring synthe ti see line aren
Polyesters in bulk

The priority of filing in Great Britain on March 26, 1965 and H.3.1986 is used

The invention relates to a dyeing process, in particular a process for "bulk dyeing of synthetic linear polyesters, particularly polyethylene terephthalate.

When dyeing synthetic linear polyesters in bulk, the dye used must meet the following requirements comply to achieve perfect products; 1.) The dye must be the high temperature of the melted Materials can withstand (29O ° C);

2.) It must not be very volatile, otherwise it could sublime during melt spinning, which is uneven Coloring would result, and because the fabrics lose their color intensity when they are subsequently pleated or could rub off on adjacent fabric; 3.) It must be lightfast and extremely durable exhibit against skin exhalation, bleach and dry cleaning solvents.

It has been found that for dyeing synthetic linear polyesters in bulk a genus heterocyclic dye compounds is particularly suitable.

^ According to the invention, a method for dyeing

* o suggested synthetic linear polyesters in bulk

** ► that consists in the fact that as color matter one or more

! ^ Tannins of the formula i

S E-X

can be used, where X is a group of the formula:

or -CH

represents

E is a five-membered or one-membered nitrogen-containing heterocyclic Represents a ring containing a heterocyclic nitrogen atom. holds that is attached to a carbon atom of the ring linked to X via a double bond, and that too May contain substituents or form part of a fused ring system,

the benzene ring A can also contain substituents or form part of a uaphthalene nucleus,

at least one of components X and R is substituted by at least one —COOX group, where X is a hydrogen atom or an alkyl, hydroxyalkyl, alkoxyalkyl, or hydroxyalkoxyalkyl radical represents

and 'provided that A and R are free of sulfonic acid groups are.

As examples of the substituents that can be attached to the benzene ring A, one can use chlorine or bromine atoms, lower alkoxy, such as methoxy and ethoxy, lower Mention alkyl, such as methyl, nitro or hydroxyl groups. However, it is preferred that the benzene ring A is substituted with a -COQY group.

As examples of the 5- or 6-membered heterocyclic Rings represented by R can be thiazole, oxazole, oxadiazole, pyrazole, triazole, pyridazine, pyr <=> imidine, triazine, oxazine and preferably pyridine rings mention co. As examples of the ring R containing ^ condensed ring systems can be benzoxazole, indazoi-, ^ Benziminazole, Benzthiazole, Naphthathiazole, Quin & zoline, - »Quinoxaline, phthalazine, isoquinoline, and preferably

mention cn quinoline rings.

In addition to a -COOY group, R can be chlorine or bromine atoms or Hydroxy, methyl or ethoxy groups as substituents. wear.

For the purposes of the invention, the terms "lower alkyl" and "lower alkoxy" are intended to be alkyl and alkoxy radicals, respectively mean, the ^ e contain 1 to 4 carbon atoms.

The alkyl radicals represented by Y are preferably lower alkyl radicals such as ethyl, ethyl, propyl, and butyl radicals. The hydroxyalkyl radicals represented by Y are preferably mono- or dihydroxy lower alkyl radicals such as ß-hydroxyethyl, ß- or Y-hydroxypropyl and ß, Y-dihydroxypropyl radicals. The ones represented by Y Alkoxyalkyl radicals are preferably lower alkoxy-lower alkyl radicals like ß ~ ethoxyethyl and ß- or Y-Hethoxi / testyl radicals. The hydroxyalkoxyalkyl radicals represented by X are preferably hydroxy-lower alkoxynicdrigerali: yl-x radicals like ß- (ß'-By ^ roxyäthoxy) äthyl- and β- or Y- (Y'-hydroxypropoxy) propyl radicals.

The method according to the invention can expediently thereby realizes that one / or more of the named Dyes are mixed with the synthetic linear polyesters in a manner known per se. So you can Shavings of the polyester fabric with an Ileberzug from the finely divided dye provided in varnishing drums, whereupon the resulting colored mixture is melted and :: u Inject threads or shape them into solid objects can. If desired, the tumbling process can employ a dispersion of the dye in a volatile liquid such as water or alcohol, or such a liquid can be used to moisten the dye-polymer mixture use while drumming. Preferably, the volatile liquid is allowed to evaporate before melting. One can Also blend dye with monomers or prepolymers at an appropriate stage in making the polyester.

_o Optionally one may, salt, the dyes in which Y represents a ° hydrogen atom in the form of salts, for example Ammoniumcx> use, with the result that, in the warmer treatment to melt the polyester, the free acids ^ are formed.

ο As examples of the synthetic linear polyester that

can be colored according to the process according to the invention, one polytity? mention by leaktion of terephthalic

BATH ORIGINAL

Phthalic acid with glycols of the formula: HQ- (CH ^) _x -OE, where x represents an integer from 2 to 10, or with 1,4- di (hydro23nnethyl) cyclohexane. The term "synthetic linear polyester" is also intended to include copolyesters based on the polyesters mentioned, it being possible to produce the copolyesters by replacing part of the terephthalic acid with another dicarboxylic acid or a hydroxycarboxylic acid and / or part of the glycol with another glycol replaced.

The dyeings obtained according to the invention are good Resistance to vials, steam treatments under pressure, acidic staining, skin exhalation, rubbing after treatment with steam, dry heat treatments like pleating, and light. It has also been shown that the colorations can be produced in very deep shades without that the properties of the synthetic linear polyesters or the fibers made from them are impaired.

The dyes used according to the invention can be produced in that a heterocyclic compound of the formula: E ¹ -CH- ,, where R ^{1 represents} a 5- or 6-membered nitrogen-containing heterocyclic ring which contains a nitrogen atom which is ortho to one with the

of the BioFS Methyl group connected carbon atom / Lies, which also May contain substituents or form part of a fused ring system with an anhydride of the formula:

or

is condensed, where A has the meaning given above, provided that the heterocyclic compound and the anhydride ο together have at least one -QOOY group. The color substances in which Y is not a hydrogen atom can ^ can also be generated by the fact that the corresponding carbon » k> acids (i.e. the dyes in which Y is a hydrogen atom _ »Represents) to be esterified with the corresponding alcohol«

ο As specific examples of the heterocyclic compounds of the formula R ¹ -CH, one can use 2-methylohinoline, 2,4-dimethylquinoline, 5- or 6-methyl-2-methyl-mnoline, tx-pieoline,

1594412

Mention 2-methylbenzothiazole and 2-methyl-1,3,5-triazine.

As "specific examples of the phthalic anhydrides mentioned, trimellitic anhydride, phthalic anhydride, H- Oarboxy-lje-naphthalic anhydride, 3- or 4-chlorophthalic anhydride, ^ -obromethoxyphthalic anhydride and 3- or 4-nitrophthalic anhydride can be mentioned.

If necessary, dyes can be used which im Molecule two systems of the formula:

. EX

where R and X have the meanings given above. as Examples of such dyes can be mentioned the dyes of the following formulas:

0OT

CC

0OY

00 '

0OY

ΌΟΥ

ÖOOX

Many of the dyes used according to the invention are new Compounds so that, according to a further feature of the invention, the dyes of the formula:

are created, where R has the above meaning and the Benzene ring with chlorine or bromine atoms or nitro groups may be substituted, and wherein the benzene ring and / or E is substituted by at least one -COOY group.

A preferred genus of the dyes used according to the invention consists of the dyes of the formula:

0OX

wherein the quinoline ring optionally with Ghlöratomen or Methyl, hydroxyl or -COOY groups is substituted. One Another preferred genus consists of the dyes of the formula:

ο ο to

0OY

The invention is explained below on the basis of exemplary embodiments purely for example explained in more detail, with all quantities, are based on weight * -

Example 1 * ■ : ''

A mixture of 15! Rush 2-methylquinoline and share 21.3 Trlmellithsäureanhydrid is erhitist for 2 hours at 220 ⁰ O · und..dann 4 hours on this lemperatur gehabten * i ^^ cooled, and the resulting Pestatoff

grated and in 250 parts of a 10% aqueous Dissolved sodium carbonate solution. Then the solution is filtered, and the filtrate is acidified with hydrochloric acid, whereupon the precipitated solids are filtered off, washed with water and then dried *

The analysis shows that the dye has a carbon content of 71.6%, a hydrogen content of 3.5% and a nitrogen content of 4.4%. The theoretically determined carbon, hydrogen and nitrogen content of O ₁₉ H ₁₁ O ₄ U is 71, -9%, 3.4% and 4.4%, respectively.

Example 2

IDs is 1 part of the dye according to Example 1 in Pulvex 'form. with 100 parts of polyethylene terephthalate in the form of chips mixed in the lacquering drum. Earth by melt spinning fibers are produced from the resulting mixture in a manner known per se, which have a deep greenish-yellow hue of excellent quality Show authenticity.

Example 3

A mixture of 10.2 parts of 2 ~ methyl-3-hydroxyquinoline-4-carboxylic acid, 15.5 parts of trimellitic anhydride and 100 parts of o-dichlorobenzene are refluxed for 18 hours. Then the mixture is brought to 20 ° 0, whereupon the precipitated .Dye is filtered off, washed with benzene and then dried.

in powder form 1 part of this dye / and 3 parts of ß-ethoxy,

Ethanol mixed with 100 parts of polyethylene terephthalate in the form of granules in the coating drum until a uniform mixture is obtained. The dyed mixture is ^{dried at 120 0} O in a vacuum;.: Fibers are produced therefrom by melt spinning, which have a strong green-yellow hue _o good fastness. - ...

Example 4 . .._ ■ · -

j £ j Eb, 100 parts of dimethyl terephthalate, 71 parts of ethylene - "^ glycol and 0.05 parts of manganese acetate is stirred for 4 hours at 197 ° 0 MITC" each other, to evaporate x ^ obei about 33 ropes methanol from the C ₅ mixture of the mixture. then 0.04 part of phosphorous acid, 0.05 part of antimony trioxide and 3 parts of 5-arbomethoxane are added in one hour beforehand for 30 minutes

SAD ORIGINAL ^!

Ball mill wetted in the presence of 12 parts of ethylene glycol was admitted. The! Temperature "of the mixture becomes then to 277 ° C and the pressure to 0.3 mm of mercury brought, the mixture is heated under these conditions for a further 6 hours, while the excess ethylene glycol evaporates. The melt is then processed into threads, which are subsequently drawn into fibers. The so obtained Pasers have a greenish-yellow shade of excellent fastness.

Example 5

There are 100 parts of dimethyl terephthalate, 71 parts of ethylene glycol, east, 05 parts of manganese acetate and 3 parts of 5-Carbomethoxychinphthalon stirred for 4 hours at 197 ⁰ O with each other, to evaporate off about 33 parts of methanol. Then 0.0A part of phosphorous acid and 0.05 part of antimony trioxide are added, whereupon the temperature of the mixture is brought to 277 ° C. and the pressure to 0.3 mm of mercury and the mixture is heated for a further 6 hours under these conditions , while the excess ethylene glycol evaporates. The mixture is then processed into threads that are subsequently stretched into fibers. The fibers obtained in this way have a green-yellow shade of excellent fastness.

The 5-Oa ^ bomethoxyquinphthalone used was by Treatment of ^ -carboxyquinophthalone with thionyl chloride - Generated and reaction of the resulting acid chloride with methanol.

The table below are shown further examples of the inventive Yex ^v iahrens analogous to the embodiments according to Examples 2 to 5 using the dyes can be carried out, each of the by reacting the heterocylisehen compound given in the 2nd column of the table with Anhydride or the acid of the 3rd column of the table can be generated. The 4th column of the table shows the color shade of the resulting fibers.

ΟΒΙΘΙΝΜ. XHSPBClBO

09 842 / 1850- _q

spl. ■ Heterocyclic compound anhydride or Sälire 'color

tint

2-methylbenz- (5,6) quinoline irimellitic anhydride yellow

6-chloro-2-methylquinoline dto * dto.

6-bromo-2-methylquinoline. dto. dto,

2-methylbenziinidazole dto. Dto.

2-Kethylbenzthiazol 'dto. Dto.

2-methylnaphth- (2 ', 1', 4,5) thiazole dto.-dto.

6-0hlor-2-methylbenzthiazole dto. - dtö.

2,4-Dihydroxy-6-methyl-1,3,5-triazine dto. 'Dto.

6,6'-Di (2-methylquinolyl) dto. Dto.

(2 molecular parts)

2,6-dimethylquinoline hemimellitic anhydride dto.

2-methylquinoline 4-hydroxyhemimellite dto.

acid anhydride M

2-methyl-3-hydroxyquinoline hemimellitic anhydride dto.

2-methylquinoline naphthalene-1,4,5-tri-green yellow

Example 19 carboxylic acid

Instead of that used according to one of Examples 2 to 5 The equivalent amount of the ß-Hydroxyäthylasters of quinphthalone-5-carboxylic acid is used in each case, resulting in green-yellow fibers which have excellent fastness.

The dye used in this case was prepared by reacting the sodium salt of Chinphthalon-5-carboxylic acid in ethylene dichloride at 14O ⁰ C in the presence of diethylamine generated.

Example 20A instead of the ß-hydroxyethyl ester of 0hinphthalone-5-carboxylic acid used in Example 19, equivalent amounts of

a) the ß-ethoxyethyl ester of 0hinphthalon-5-carboxylic acid,

b) the ß-hydroxyethyl ester of 3'-hydroxyquinophthalone-5-carboxylic acid,

c) the ß-hydroxyethyl ester of

If

/ ⁰ SA - coon

• ^C % JU

00 98 42/1850

- 10

d) the ß-Cß'-Hydroxyäthox ^ Oäthylester of quinphthalone-5-carboxylic acid

used, showing yellow fibers with excellent fastness result.

The dyes la) and c) have been produced by reaction of the sodium "salt of the corresponding carboxylic acid with ethylene chlorohydrin at 140 ⁰ C in the presence of diethylamine. The dye a) was produced by reacting quinphthalone - ^ - carboxylic acid with thionyl chloride and treating the resulting product with ß-ethoxyethanol, while the dye d) by reacting the sodium salt of quinphthalone-5-carboxylic acid with ß- (ß ^l -hydroxyethoxy) ethyl chloride was produced.

00984271850

-11-

Claims (1)

1. Process for dyeing synthetic linear polyesters in the mass, characterized in that as color matter one or more dyes of the formula: EX be used ,, where
X is a group of the formula: -CH CG or represents R is a 5- or G-membered nitrogen-containing heterocyclic Represents ring containing a heterocyclic nitrogen atom, which is bonded to a carbon atom of the ring connected to X via a double bond, and which is also May contain substituents or form part of a fused ring system, the benzene ring A can also contain substituents or form part of an ITaphthalene nucleus, at least one of components X and R with at least one -COOT group, where X is a hydrogen atom or an alkyl, hydroxyalkyl, alkoxyalkyl, or hydroxyalkoxyalkyl radical represents and provided that A and R are free of sulfonic acid groups. 2. The method according to claim 1, characterized in that as a dye of the formula: ■ R-CH ^X is used, where A and JL are those given in, Amnaruch 1 Have meanings. BAD OFHQINAl. Method naoii claim 1 or 2, characterized. that a dye of the formula: -COOT is used, the Öhinolinring optionally with Chlorine atoms or methyl, hydroxyl or -GGOT groups is substituted, where Y is given in claim T. Has meaning 4. The method according to claim 1 or 2, characterized in that that a dye of the formula: OH I f- 0001 A * ³ is used, in the case of Y that given in claim 1 Has meaning. 5-, method according to any one of claims 2 to 4, characterized characterized in that the -GGOY group is the Gai'boxylic acid group represents 6. Method according to one of claims 1 to 5, characterized in that each dye is mixed with the polyester and the resulting mixture is processed into fibers by melt spinning. 7, method according to one of claims 1 to 5, dadiirch auieimot- that the dye with a tlonomer or Vor «j-οH ₁ ) Wt-J 'ü (fi rol ^ oöterr- vcrrair.cüit, dar» auacliliecrvenci iii . that BoI ^ ort..r ui \ .eseti; t rliv. BATH 009842/1850 ^ö